KR102242079B1 - Cellulose-containing paint systems - Google Patents

Abstract

The present invention comprises a) chemically unmodified cellulose, b) optionally polyolefin wax and/or Fischer-Tropsch wax and/or amide wax and/or biological wax, c) film former and d) optionally solvent or water, e) optionally pigments, and f) optionally volatile and/or nonvolatile additives, wherein the chemically unmodified cellulose has an average fiber length of 7 to 100 μm and an average aspect ratio of less than 5. will be.

Description

Cellulose-containing paint systems {CELLULOSE-CONTAINING PAINT SYSTEMS}

The present invention relates to a chemically unmodified cellulose-containing paint system, and also the use of cellulose/wax formulations in paints to improve sedimentation and redispersion behavior, and to significantly improve scratch resistance and tactility. It is about.

It is understood that the paint will generally be a coating material with a specified set of properties according to DIN EN 971-1. As a coating in the form of a liquid, paste or other powder, the paint has the function of creating a visual concealing coating with decorative properties, protective properties, and also optionally, certain industrial properties, according to the above standards. Among the mentioned systems, paints can be classified according to the properties of the film former (alkyd resin paint, acrylate resin paint, cellulose nitrate paint, epoxy resin paint, polyurethane resin paint, etc.). Binders are defined as pigment-free and filler-free fractions of a coating that is dried and/or cured according to the above standard. Therefore, the binder consists of a film forming agent and a non-volatile fraction of the additive. Non-dried and/or uncured paint systems are generally composed of film formers such as epoxy resins, polyester resins, polyurethanes, cellulose derivatives, acrylate resins, etc., optionally with solvents, additives, fillers and pigments. It consists of the same additional ingredients. Solvent-free systems are completely solvent-free, for example for film formers (eg liquid monomers) that are commonly used as dispersion-based paints, on an aqueous basis, or already in liquid form. The paint system is further mixed with additives to produce the desired service properties. Thus, for example, micronized wax is added to impart improved scratch resistance, matting, resistance to abrasion and resistance to metal marking to the painted surface (see, for example, the following: Fette, Seifen, Anstrichmittel 87, No. 5, pages 214-216 (1985)]. Similar effective protection of the paint surface is achieved by applying a specific silicone, which, similar to wax, lowers the coefficient of sliding friction of the dried paint, thereby reducing blocking phenomena and thus improving scratch resistance. (See: Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 18, Section 4.3 Paints & Coatings, Weinheim, 1991, pages 466). Scratch resistance is mechanically stressed paint systems and paint coats (for example, in the case of floors and furniture, for example desks, dining tables, etc., or in the case of various commodity products, for example toys. coat) is especially important. However, especially in the case of the floor, in addition to scratch resistance, a sense of stability of the foot and thus a reduction in the risk of slipping-that is, an increase in the sliding friction coefficient also plays an important role. For everyday products and furniture surfaces, a pleasing texture is often desirable. In contrast to the sliding friction and scratch resistance that can be quantified by measurement, texture can only be measured qualitatively. As a measure of touch, terms such as “soft” (soft feel), velvety, smooth, coarse, hard, and the like are used. The soft touch/feel effect is obtained in common paint systems by adding a specific wax or silicone, or directly by means of a highly flexible polyurethane binder. Here, the soft or velvety feel is usually directly contradictory to the required scratch resistance. Especially in the case of painted wooden surfaces, moreover, artificial and artificial textures often lead to subjective degradation of quality by the user. The requirement is, instead, for a painted surface with a texture that corresponds to that of natural wood.

In the market, there is a demand for a painted surface having a soft and natural tactile feel with long-term robustness in use, which is generally achieved by improving scratch resistance. It is difficult to combine both properties together in a paint system.

The use of cellulose in paints has so far been limited to cellulose derivatives. The reason is that cellulose is absolutely insoluble in all common organic solvents and especially water. Therefore, so far, only cellulose derivatives have been used in paints (see BASF Handbook, Lackiertechnik, Vincentz-Verlag, 2002, Section on Raw Materials, page 45). In particular, cellulose nitrates and cellulose esters have been described a lot as adjuvants in paint systems and also as film formers. For example, cellulose can be modified with different levels of esterification with organic and inorganic acids to form cellulose nitrate and also acetic acid, propionic acid and butyric acid esters. Esters of cellulose with organic acids differ from cellulose nitrates, in particular due to improved light stability and reduced flammability. In addition, cellulose esters are distinguished by thermal stability and low temperature stability, which are improvements to the thermal stability and low temperature stability of cellulose nitrate, but this comes at the expense of poorer miscibility with other resins and organic solvents. This disadvantage can be compensated to some extent through the use of mixed esters.

Cellulosic fillers are typically used in the form of methyl or ethyl ether to control the rheological properties of liquid paint systems. Conversely, little is known about the use of chemically unmodified cellulose in paints. For example, WO 2011/075837 describes nanocrystalline cellulose and silanized nanocrystalline cellulose for paint applications. Nanocrystalline cellulose (NCC) is obtained from purified cellulose, which is obtained by acidic hydrolysis and subsequent dispersion, for example under sonication. Cellulosic fibers, which are thus decomposed into individual fibrils, have a diameter of 5 to 70 nm and a length of 250 nm or less. However, a reduction in the matting effect and hydrophobic properties of the surface as well as a reduction in the scratch resistance of the polyurethane paint used was observed through the use of nanocrystalline cellulose. This effect could only be compensated or overcompensated by the use of silanization and thus chemically modified nanocrystalline cellulose.

WO 2010/043397 mentions the use of ultrafine cellulose as an additive for coatings. This cellulose also represents very fine cellulose particles with a diameter of 20 nm to 15 μm. With the use of ultrafine cellulose, a matting effect and increased scratch resistance for a part of the coated surface were obtained.

Additionally, due to the insolubility of cellulose and the difference in density to the film former, cellulose-containing paint systems are prone to unstable and rapid sedimentation. This is especially the case for low viscosity paint systems. The separation that occurs when storing the paint system makes the paint system more difficult to handle. The sediment formed after a short time, consisting mainly of cellulose, is extremely compact and very difficult to redisperse.

Therefore, there are serious drawbacks to the use of chemically unmodified cellulose as an additive component in paint systems, and thus there is a need to improve these drawbacks.

Surprisingly, a paint system using chemically unmodified cellulose with a defined average fiber length and a defined average aspect ratio imparts a natural soft texture in appearance, and also exhibits improved scratch resistance to parts of the coating, and polyethylene It has been found that when combined with waxes and/or Fischer-Tropsch waxes and/or amide waxes and/or biological waxes, unpredictable stabilization of the paint formulation against sedimentation is obtained.

Additionally, by using such a formulation, it was surprisingly possible to achieve a significant improvement in scratch resistance.

Therefore, the subject of the present invention

a) chemically unmodified cellulose,

b) optionally polyolefin waxes and/or Fischer-Tropsch waxes and/or amide waxes and/or biological waxes,

c) a film former,

d) optionally a solvent or water,

e) optionally a pigment, and

f) a paint system optionally comprising volatile and/or nonvolatile additives,

The chemically unmodified cellulose has an average fiber length of 7 to 100 μm, preferably 15 to 100 μm, more preferably 15 to 50 μm, and an average aspect ratio of less than 5 paint systems.

A further subject of the invention is a method of improving the sedimentation and redispersion behavior, and scratch resistance of a paint system, the paint system comprising at least one polyolefin wax and/or Fischer-Tropsch wax and/or amide wax and/or Bio-based wax, and chemically unmodified cellulose having an average fiber length of 7 to 100 μm, preferably 15 to 100 μm, more preferably 15 to 50 μm and an average aspect ratio of less than 5, is a method. The paint system may further comprise pigments and solvents or water, and also additional volatile and/or nonvolatile additives.

Through the addition of chemically unmodified cellulose having an average fiber length of 7 to 100 μm, preferably 15 to 100 μm, more preferably 15 to 50 μm and an average aspect ratio of less than 5, compared to a coating without adding cellulose Considering that it is possible to achieve the improvement of the scratch resistance and texture of the coating, the present invention is a method for further improving the scratch resistance of the coating (fully cured paint system) and obtaining a smooth texture, the paint The system relates to a method of mixing with chemically unmodified cellulose having an average fiber length of 7 to 100 μm, preferably 15 to 100 μm, more preferably 15 to 50 μm and an average aspect ratio of less than 5.

The paint system may further comprise pigments and solvents and/or water and and as well as additional volatile and/or nonvolatile additives.

The pigments, film formers, auxiliary and solvents contemplated are, in principle, described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 18, section on Paints & Coatings, Weinheim, 1991, page 368ff] or as described in BASF Handbook, Lackiertechnik, Vincentz-Verlag, 2002, section on Raw Materials, page 28ff. .

Binders are understood analogously to DIN 971-1 as constituting the pigment-free and filler-free fractions of the dried and/or cured coating. In addition to the film former, it further comprises other non-volatile additives. The coating is understood to be a fully cured and/or dried paint system (see BASF Handbook, Lackiertechnik, Vincentz-Verlag, 2002, section on Raw Materials, page 26).

Suitable film formers according to the present invention are both polyurethane-based resins and epoxy-based resins, which are in a one-component as well as two-component form. Further suitable film formers include, in addition to cellulose derivatives such as cellulose nitrates and cellulose esters, for example alkyd resins and also acrylate based resins such as polymethyl methacrylate.

The epoxy-based film forming agent, together with an additional reactant (curing agent), at least a bifunctional epoxide-containing monomer such as bisphenol A bisglycidyl ether, diglycidyl hexahydrophthalate, or the like, or a prepolymer or It is a polyaddition resin crosslinked through a macromonomer. It is therefore typically processed as a two-component resin. Typical curing agents are amines, acid anhydrides, or carboxylic acids. The amines used are often aliphatic diamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, and the like, and also alicyclic amines, such as isophoronediamine, or the like, or aromatic diamines such as 1, 3-diaminobenzene and the like. The acid anhydride used includes, for example, a diester of phthalic anhydride or trimellitic anhydride. Epoxy-based film formers of this kind and their application to paints, and also suitable solvent-based, solvent-free and water-based embodiments are described in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 18, Paints & Coatings, section 2.10, Weinheim, 1991, pages 407-412.

Polyurethane-based film formers are likewise polyaddition resins, which are reacted with polyhydric alcohols from isocyanate-containing monomers. Depending on the chemical composition of the resin, one-component PU paint and two-component PU paint are distinguished. Typical isocyanate-containing monomers are, for example, toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (PMDI), hexamethylene diisocyanate (HDI), isophorone di. It is based on isocyanate (IPDI). Polyols are commonly used as polyester polyols, acrylic acid copolymers and polyether polyols with different complexity. PU resins are solvent-containing, solvent-free and also exist as aqueous systems. PU resins for paints are described in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 18, Paints & Coatings, section 2.9, Weinheim, 1991, pages 403-407.

Polyester can be divided into saturated polyester binders and unsaturated polyester binders. Polyester binders are from polyhydric carboxylic acids such as terephthalic acid, isophthalic acid, trimellitic acid, adipic acid, sebacic acid, dimer fatty acids and the like and from polyols such as ethylene glycol, diethylene glycol, glycerol, butanediol, It is formed from hexanediol, trimethylolpropane, and the like. Depending on the rigidity of the dicarboxylic acid and polyol, the mechanical properties can vary from soft to hard. The unsaturated polyester further has a polymeric vinyl group, which can be crosslinked through UV light or a radical initiator. Paint polyesters are described in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 18, Paints & Coatings, sections 2.6 & 2.7, Weinheim, 1991, pages 395-403.

Alkyd resins belong to the group of polyesters. They are divided into air-drying and oven-drying systems, depending on their drying mechanism. In chemical terms, alkyd resins are polybasic acids such as polybasic acids such as phthalic acid, phthalic anhydride, terephthalic acid in the presence of oils and/or unsaturated fatty acids such as linoleic acid, oleic acid, etc. It is formed by reaction with etc. Alkyd resins are mixed with a crosslinking-promoting catalyst, commonly referred to as a siccative. Alkyd resins and embodiments thereof are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 18, Paints & Coatings, section 2.6, Weinheim, 1991, pages 389-395.

The most important cellulosic film formers include cellulose nitrates and cellulose esters such as cellulose acetate, cellulose acetobutyrate and cellulose propionate. The raw material of this cellulose derivative is purified natural cellulose, which is usually obtained directly from wood. Examples of the derivatizing agent are nitrating acid and, for example, anhydrides of acetic acid, propionic acid and butyric acid. In contrast to chemically untreated cellulose, cellulose derivatives are soluble in organic solvents, especially acetone and ethyl acetate. Cellulose derivative film formers are described in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 18, Paints & Coatings, section 2.6, Weinheim, 1991, pages 369-374.

Industrially, cellulose is of particular interest because of its very immediate availability. Cellulose is the most frequently occurring organic compound in nature and is therefore also the most commonly used polysaccharide. As a renewable raw material, it constitutes about 50% by weight of the main component of the plant cell wall. Cellulose is a polymer composed of monomeric glucose, which is linked through β-1,4-glucose bonds and consists of hundreds to tens of thousands of repeating units. The glucose molecules in cellulose are each twisted 180° with respect to each other. This makes the polymer linear, as opposed to, for example, glucose polymer starch. The industrial use of cellulose as a raw material in the chemical industry extends to various fields of application. Its physical use includes its use in paper making and also as a raw material for the production of clothing. The raw materials of cellulose mainly used for this purpose are wood and cotton.

In wood, cellulose is particularly present in the form of microscopic crystalline microfibrils, which aggregate through hydrogen bonding to form macrofibrils. Together with hemicellulose and lignin, these macrofibrils form the cell walls of plant cells.

Cellulose is obtained industrially from wood through various cellular digestion procedures. In this procedure, lignin and hemicellulose are destroyed and dissolved. Among the chemical cooking procedures, a sulphate process (alkaline) and a sulfite process (acidic) are distinguished. For example, in the sulfite process, wood chips are cooked with water and sulfur dioxide (SO ₂ ) at elevated temperature under increased pressure. In this operation, lignin is cleaved by sulfonation and converted into a water-soluble salt, lignosulfonic acid, which is easy to remove from the fiber. Depending on the pH prevailing in wood, the hemicellulose present is converted to sugar by acidic hydrolysis. The cellulose obtained from this process can then be further modified or derivatized chemically. Alternatively, after washing, a chemically untreated filler can be obtained. Other, less pronounced cooking procedures are based on mechanical and thermomechanical procedures and also thermochemical mechanical cooking procedures.

For the purposes of the present invention, the cellulose in this cooking procedure is not chemically modified. See Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 5, Weinheim, 1986, section on Cellulose, pages 375ff] contains a more detailed description of cellulose.

Suitable cellulose in the sense of the present invention is chemically unmodified cellulose having a particle size of D99≦100 μm, preferably D99≦50 μm as measured by laser diffraction. The number D99 represents the maximum particle size present in the particle mixture. The corresponding cellulose powder is also optionally obtained from the coarser cellulosic material by fractionation, for example screening, or sieving, for example micronization. Cellulose is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 5, Weinheim, 1986, section on Cellulose, pages 375ff.

Chemically unmodified cellulose is used in an amount of 0.1 to 12% by weight, preferably 0.2 to 6% by weight, more preferably 1.0 to 2.0% by weight, based on the paint system.

Synthetic hydrocarbon waxes, such as polyolefin waxes, are suitable wax components. These waxes can be produced by thermal decomposition of branched or unbranched polyolefin polymers or by direct polymerization of olefins. Examples of suitable polymerization processes include radical processes, wherein olefins, generally ethylene, react at high pressure and high temperature to form polymer chains to some degree of branching; Moreover, ethylene and/or higher 1-olefins, such as propylene, 1-butene, 1-hexene, etc., are polymerized using organometallic catalysts such as Ziegler-Natta or metallocene catalysts to be unbranched or The process of forming the branched wax is contemplated. Corresponding methods for the preparation of olefin homopolymers and copolymer waxes are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 28, Weinheim, 1996, sections 6.1.1./6.1.2. (high pressure polymerization, wax), section 6.1.2. (Ziegler-Natta polymerization, polymerization using metallocene catalysts), and section 6.1.4. (Pyrolysis)].

Additionally, a wax known as Fischer-Tropsch wax can be used. These waxes are catalytically produced from the synthesis gas and differ from polyethylene waxes in lower average molar mass, narrower molar mass distribution and lower melt viscosity.

The hydrocarbon wax used may not be functionalized or may be functionalized through polar groups. The introduction of such polar functional groups is by the corresponding modification of the non-polar wax, e.g., air of polar olefin monomers, e.g. α,β-unsaturated carboxylic acids and/or derivatives thereof, e.g. acrylic acid or maleic anhydride. It can be achieved subsequently by oxidation or grafting-on. In addition, the polar wax is copolymerized with ethylene and a polar comonomer such as vinyl acetate or acrylic acid; It can additionally be produced by oxidative decomposition of non-waxed ethylene homopolymers and copolymers having a higher molecular mass. Corresponding examples are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 28, Weinheim, 1996, section 6.1.5.

Further suitable polar waxes are, for example, amide waxes, as obtainable by reaction of relatively long chain carboxylic acids, for example fatty acids with monofunctional or polyfunctional amines. Fatty acids typically used for this purpose have a chain length in the range of 12 to 24 carbon atoms, preferably 16 to 22, and may be saturated or unsaturated. Fatty acids preferably used are C ₁₆ and C ₁₈ acids, more particularly palmitic acid and stearic acid or mixtures of both acids. Besides ammonia, suitable amines are especially polyvalent organic amines, examples being difunctional organic amines, in which case ethylenediamine is preferred. It is a standard commercial product of the trade name EBS wax (ethylenebisstearoyldiamine), and the use of waxes produced from industrial stearic acid and ethylenediamine is particularly preferred.

Moreover, it is possible to use biological waxes, which are generally polar ester waxes. Biological waxes are generally understood to be waxes based on renewable raw material principal components. These can be both natural ester waxes and chemically modified ester waxes. Conventional natural biological waxes are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 28, Weinheim, 1996, section 2 (Waxes). These include, for example, palm wax, such as carnaver wax, grass wax, such as candelilla wax, sugarcane wax and straw wax, beeswax, rice wax, and the like. Chemically modified waxes are those derived from fatty acids based on vegetable oils, typically by esterification, transesterification, amidation, hydrogenation, and the like. These include, for example, metathesis products of vegetable oils.

Biological waxes also include Montan wax in unmodified, refined and/or derivatized form. Detailed information on such waxes can be found in, for example, Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Edition, Vol. A 28, Weinheim, 1996, section 3 (Waxes).

There are various methods suitable for incorporating wax into a paint system. For example, the wax can be dissolved hot in a solvent and then cooled to produce a finely divided, liquid dispersion or composition having a pastelike consistency, which is blended with a paint system. It is also possible to polish the wax in the presence of a solvent. According to one dissemination technique, the wax is also agitated into the paint formulation as a solid, in the form of an ultra-fine powder ("micronide"). Ultrafine powders are produced by grinding, for example in air jet mills, or by spraying. The average particle size (D50 or median size) of these powders is generally in the range of 5 to 15 μm. The D99 for the wax micronized material used is retained at 100 μm or less, preferably 60 μm or less, and more preferably 50 μm or less. For the possibility of grinding to microns, the hardness or brittleness of the wax product should not be too low.

Wax is used in an amount of 0.1 to 12.0% by weight, preferably 0.2 to 6.0% by weight, more preferably 1.0 to 2.0% by weight, based on the paint system.

Chemically unmodified cellulose can be incorporated by dispersion before or after addition of the paint system and wax; It is also possible to add together by incorporating a mixture of micronized wax and unmodified cellulose. It has proven particularly advantageous to micronize the unmodified cellulose and wax together and use them in the form of micronized mixtures. Here too, the micronized mixture can be incorporated by dispersion either before or after the addition of the printing ink system. Dispersion methods are known to those skilled in the art; In general this is done using a high speed stirring or mixing element, for example a Mizer disk or a dissolver disk.

Chemically unmodified cellulose in liquid paint systems exhibits a reduced sedimentation tendency by combination with polyolefin waxes and/or Fischer-Tropsch waxes and/or amide waxes and/or biological waxes; The precipitated sediment can be redispersed more easily. In addition, the set paint exhibits remarkable scratch resistance.

The paint system of the present invention comprises additional volatile and nonvolatile additives such as plasticizers, crosslinkers, crosslinking accelerators, UV stabilizers, antioxidants, surfactants, wetting aids, antifoaming agents, thixotropic aids and other auxiliaries. May be included in a conventional addition concentration.

The paint system of the present invention has proven to be particularly suitable for use as wood paint, more particularly wood paint for the painting of wood furniture, wood floors and wood products of any kind. The use of chemically unmodified cellulose having dimensions according to the invention results in a soft to wood-like and natural touch (texture), in contrast to unfilled paints.

The examples below illustrate the invention in more detail, but do not limit the invention to these examples.

Example:

Performance test

The raw materials used for the chemically unmodified cellulose of the present invention were Arbocel UFC M8, Arbocel BE 600-30 PU and Arbocel BWW 40. As a comparative material, corn starch particles (manufactured by Roquette GmbH) were used, which were particle size fractionated by screening. Among other factors, testing for different particle size distributions was thus possible. Avocel products likewise differ in their particle size distribution.

The waxes used were the following commercial products from the family of Clariant Produkte (Deutschland) GmbH:

-Ceridust 2051: Micronized Fischer-Tropsch wax; D99 <50 μm,

-Ceridust 3620: micronized polyethylene wax; D99 <50 μm,

-Ceridust 5551: micronized montan wax; D99 <50 μm.

Characteristic particle sizes D50, D90 and D99 were determined according to ISO 13320-1 based on laser diffraction measurements by Mastersizer 2000 (Malvern). For this, the samples were pretreated with a dry dispersion unit (Scirocco 2000).

Measurement of scratch resistance

For the measurement of scratch resistance, the paint system under test was applied to the glass surface and tested using a hardness test rod (manufactured by Erichsen, TYPE 318). Using a Bosch engraver with a diameter of 0.75 mm and a hardness test rod, scratch resistance was measured by a method based on DIN ISO 1518. The scratch track should be about 10 mm long, leaving a distinct mark on the paint. By adjusting the spring tension, different forces can be exerted on the painted surface. The force required to leave a distinct mark on the paint was measured for a wide variety of paint formulations.

Evaluation of texture

The texture of the individual painted surfaces was evaluated by rubbing with the back of the hand. In addition, the evaluation was conducted by 20 individuals to obtain independent opinions. The ratings listed in the tables correspond to the majority of comments.

Measurement of sliding friction coefficient

The sliding friction coefficient was measured using a model 225-1 friction peel tester (manufactured by Thwing-Albert Instruments Company) in a method based on the method of ASTM D2534. To this end, a glass plate coated with a paint under test was applied to the analysis instrument. Thereafter, a leather-coated metal carriage (349 g) was placed on the coated surface. Thereafter, the carriage was pulled at a constant speed (15 cm/min) onto the coated glass surface. The force required to pull the carriage was measured. Since what was confirmed was the dynamic sliding friction coefficient, it was possible to ignore the initial force required to initiate the carriage movement.

Test of sedimentation and redistribution behavior

In the measuring cylinder, 4 g of each sample to be investigated was dispersed in 200 g of a two-component solvent-containing polyurethane paint (2 K PUR) and in 200 g of butyl acetate; The dispersion was left to stand. The layer thickness of the settled precipitate was read after the specified time interval. The smaller the value read, the denser the sediment and the higher the sedimentation tendency. The measuring cylinder was carefully swirled to test the redispersibility of the sediment. Table 2 shows the results.

As shown in Table 2, the thicker the sediment, the more effectively the particles can be redispersed. In both systems, natural corn starch forms a dense sediment that is difficult to redisperse. In both systems, the powder mixture of natural cellulose Avocel BE 600-30 PU and polyethylene wax showed significantly reduced sedimentation tendency and best redispersibility. Natural cellulose Avocel BE 600-30 PU alone showed an improved sedimentation tendency. In 2K PUR paints, redispersibility was difficult to achieve, but was readily possible in butyl acetate.

Tests in two-component solvent based polyurethane paints:

PUR paints with the following composition were used:

Formulation:

The described paint system is mixed with 2% or 4% micronide (wax or cellulose or wax/cellulose mixture) and applied to the glass surface with a doctor blade (60 μm). After a drying time of 24 hours, and after storage for 24 hours in a conditioning chamber thereafter, the scratch resistance and sliding friction coefficient can be measured. The values are shown in Table 3.

At 0.1N, the scratch resistance of the polyurethane paint described above (Example 3) is very low. By adding Avocel's Avocel UFC M8 and Avocel BE 600-30 PU (Examples 22 to 25), it was possible to achieve a remarkable increase in scratch resistance. Specifically, Avocel BE 600-30 PU (Examples 24 and 25) raises the scratch resistance of the paint used to a particularly high degree. Through the use of a wax/cellulose mixture (Examples 12-15), the scratch resistance of the paint system is further increased.

The addition of chemically unmodified cellulose with a defined fiber length and a defined aspect ratio to the described paint system has a positive effect on its texture. Both of the paint systems described in Examples 22 and 23 containing Arvocel UFC M8 as an additive component are particularly noted for their soft tactile texture. Addition of Avocel BE 600-30, in contrast, produced a wood-like natural texture.

When the described paint system is mixed with a combination of cellulose and wax (Examples 12 to 15), the texture of the obtained paint corresponds to the texture of the corresponding cellulose-containing paint. Moreover, through the combination of cellulose and wax, the scratch resistance is significantly improved in the manner described above, especially in Examples 14 and 15, creating a natural wood-like texture with greatly increased scratch resistance.

Avocel BWW 40 was not tested in combination with wax since it could not be applied without problems due to the size of the cellulose particles. Since the paint surface was very heterogeneous, it was also not possible to measure the value for scratch resistance when using 4% Avocel BWW 40 (Example 27).

The application of micronized wax to the described paint system achieves the desired increase in scratch resistance through a reduction in the sliding friction coefficient (Examples 8-15). This is not required, for example in the case of floor coverings.

The addition of chemically unmodified cellulose to the described paint system leads to an increase in the scratch resistance of the paint with only a slight decrease in the sliding friction coefficient (Examples 26-29). This positive effect is also achieved when chemically unmodified cellulose is used in combination with micronized wax (Examples 16-19).

Tests in water-based polyurethane paints:

PUR paints with the following composition were used:

Formulation

This paint system was also mixed with 2% or 4% micron and applied to the glass surface with a doctor blade (60 μm). After 24 hours of drying time and 24 hours of storage in the conditioning chamber thereafter, it was possible to measure the scratch resistance and the coefficient of sliding friction. These values are shown in Table 4.

By adding Avocel UFC M8 and Avocel BE 600-30 PU to the paint system (Examples 47 to 50), an increase in scratch resistance was achievable. The texture of the resulting paint system varies depending on the size of the cellulose microns used. The somewhat coarser Avocel BE 600-30 PU variant imparts a natural wood texture. The combination of Arbocel and wax gives the best results in terms of scratch resistance. The texture of the paint to which the mixture of cellulose micronide and wax micronide was applied was similar to that of the paint modified only by applying the Avocel product. Through the combination of wax micronide and cellulose micronide, with the described paint system, it is possible to realize a natural wood texture with increased scratch resistance.

Again in this system, Avocel BWW 40 again caused application problems due to the size of the cellulose particles, so it was not tested in combination with a wax. Similar to the solvent-based system, at a concentration of 4% Arvocel BWW 40, the scratch resistance value could not be observed because the paint surface was very heterogeneous (Example 52).

The addition of chemically unmodified cellulose to the described system results in an increase in the scratch resistance of the paint with only a slight decrease in the coefficient of sliding friction of the paint (Examples 51-54). This positive effect is also achieved when chemically unmodified cellulose is used in combination with micronized wax (Examples 41 to 44).

Tests in water-based acrylic paints:

Acrylic paints having the following composition were used:

Formulation

Produce:

Part 1 was stirred for about 10 minutes at about 1500 rpm in the dissolver. Thereafter, the ingredients from Part 2 were added individually and successively and dispersed for 10 minutes at about 2000 rpm. Part 3 was added to the dissolver at about 1000 rpm. Finally, wax, cellulose or starch (2% and 4%) were incorporated at 1500 rpm and stirred for 20 minutes.

This paint was also applied to the glass surface with a doctor blade (60 μm) according to its manufacturing method. After 24 hours of drying time and then 24 hours of storage in the conditioning chamber, it was possible to measure the scratch resistance and the coefficient of sliding friction.

Claims (15)

As a paint,
a) chemically unmodified cellulose,
b) at least one wax selected from the group consisting of polyolefin wax, Fischer-Tropsch wax, amide wax, and biobased wax, and
c) a film former,
The paint may further include at least one of at least one additive selected from d) a solvent or water, e) a pigment, and f) a volatile additive and a nonvolatile additive,
The chemically unmodified cellulose has an average fiber length of 7 to 100 μm, an average aspect ratio of less than 5,
The wax is used in a micronized form having a D99 of 100 μm or less. The paint according to claim 1, wherein the chemically unmodified cellulose is used in an amount of 0.1 to 12.0% by weight, based on the paint. The paint according to claim 1, wherein the wax is used in an amount of 0.1 to 12.0% by weight, based on the paint. The paint according to claim 2, wherein the wax is used in an amount of 0.1 to 12.0% by weight, based on the paint. The method according to any one of claims 1 to 4, wherein the film forming agent is an epoxy resin group (1- or 2-component), a polyurethane group (1- or 2-component), an acrylate resin group, or a cellulose derivative group. , A cellulose nitrate group, a cellulose ester group, or an alkyd resin group. As a method of improving the texture (tactility) and scratch resistance of the paint, the paint is at least one selected from the group consisting of polyolefin wax, Fischer-Tropsch wax, amide wax, and biobased wax. Mixed with wax, and chemically unmodified cellulose having an average fiber length of 7 to 100 μm and an average aspect ratio of 5 or less,
The method, wherein the wax is used in a micronized form having a D99 of 100 μm or less. As a method of improving the sedimentation and redistribution behavior and texture and scratch resistance of paint, the paint is selected from the group consisting of polyolefin wax, Fischer-Tropsch wax, amide wax, and biobased wax. Mixed with at least one wax, and chemically unmodified cellulose having an average fiber length of 7 to 100 μm and an average aspect ratio of 5 or less,
The method, wherein the wax is used in a micronized form having a D99 of 100 μm or less. The method according to claim 6 or 7, wherein the chemically unmodified cellulose is used in an amount of 0.1 to 12.0% by weight, based on the paint. The method according to claim 6 or 7, wherein the wax is used in an amount of 0.1 to 12.0% by weight, based on the paint. The method according to any one of claims 1 to 4, wherein the paint is a crosslinking agent, a crosslinking accelerator, a flow control aid, a wetting aid, an antifoaming agent, a plasticizer, a pigment, a UV stabilizer, an antioxidant and other auxiliary agents. A paint used with at least one of a volatile additive and a non-volatile additive selected from the group consisting of ). The method of claim 6 or 7, wherein the paint is a volatile additive selected from the group consisting of a crosslinking agent, a crosslinking accelerator, a flow control aid, a wetting aid, an antifoaming agent, a plasticizer, a pigment, a UV stabilizer, an antioxidant, and other preparations. Used with at least one of the volatile additives. delete delete delete delete